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Polymer ◽  
2022 ◽  
pp. 124534
Author(s):  
Liuyong Zhu ◽  
Jingqing Li ◽  
Hongfei Li ◽  
Binyuan Liu ◽  
Jizhong Chen ◽  
...  


Soft Matter ◽  
2022 ◽  
Author(s):  
Mukul Tikekar ◽  
Kris T. Delaney ◽  
Michael Villet ◽  
Douglas R. Tree ◽  
Glenn H. Fredrickson

A facile way to generate compatibilized blends of immiscible polymers is through reactive blending of end-functionalized homopolymers. The reaction may be reversible or irreversible depending on the end-groups and is...



2021 ◽  
pp. 009524432110635
Author(s):  
Yong-Chan Chung ◽  
Ji Hu Kim ◽  
Ji Eun Park ◽  
Byoung Chul Chun

Poly(dimethylsiloxane) (PDMS) was grafted onto polyurethane (PU), and Epichlorohydrin and Bisphenol A were attached to the free ends of PDMS groups and used to link the grafted PDMS to thereby introduce flexible crosslinks between the PU chains. The flexible crosslinks enhanced the crosslink density and solution viscosity of PU but did not change the melting and crystallization behaviors of the soft segments of PU. In particular, the flexible PDMS crosslinks increased the maximum tensile stress by up to 300% and the maximum tensile strain up to 180%. The shape recovery capability at 10°C and the shape retention capability at −25°C were maintained above 90% with the flexible crosslinking. Grafted PDMS moderately improved the low-temperature flexibility of PU due to its flexibility at low temperature. The flexible crosslinks of grafted PDMS successfully improved the tensile strength, shape recovery, and low-temperature flexibility of the PU.



Catalysts ◽  
2021 ◽  
Vol 11 (12) ◽  
pp. 1554
Author(s):  
Tian Xing ◽  
Mark R. J. Elsegood ◽  
Sophie H. Dale ◽  
Carl Redshaw

The reaction of [Mo(η-C5Me5)Cl4] with the ortho-, meta-, or para-iodo-functionalized anilines 2-IC6H4NH2, 3-IC6H4NH2, 4-IC6H4NH2 yields imido or amine products of the type [Mo(η-C5Me5)Cl2(IC6H4N)] (2-I, 1, 3-I, 3, 4-I, 5) or [Mo(η-C5Me5)Cl4(IC6H4NH2)] (3-I, 2, 4-I, 4), respectively, depending on the reaction stoichiometry/conditions; we were unable to isolate an amine complex of the 2-I derivative. The reaction of [Mo(η-C5Me5)Cl4] with one equivalent of 2-I,4-FC6H3NH2 in the presence of Et3N afforded [Mo(η-C5Me5)Cl2(2-I,4-FC6H3N)]·MeCN (6·MeCN), which, upon exposure to air, afforded the Mo(VI) imido complex [Mo(η-C5Me5)Cl3(2-I,4-FC6H3N)] (7). For comparative studies, the structure of the aniline (C6H5NH2)-derived complex [Mo(η-C5Me5)Cl2(2-C6H3N)] (8) has also been prepared. The molecular structures of 1–8 have been determined and reveal packing in the form of zig-zag chains or ladders. The complexes catalyze, in the presence of benzyl alcohol under N2, the ring-opening polymerization (ROP) of ε-caprolactone affording relatively low molecular weight products. The MALDI-ToF spectra indicate that a number of polymer series bearing a variety of end groups are formed. Conducting the ROPs as melts or under air results in the isolation of higher molecular weight products, again bearing a variety of end groups. Kinetic studies reveal the aniline-derived imido complex 8 performs best, whilst a meta-iodo substituent and a Mo(V) centre are also found to be beneficial. The structures of the side products 2-IC6H4NH3Cl and 3-IC6H4NH3Cl are also reported.



Author(s):  
Hui Xing ◽  
Alireza Azizi ◽  
Roya Momen ◽  
Tianlv Xu ◽  
Steven Kirk ◽  
...  

We investigate the presence of helical character and chirality using a vector-based charge density perspective instead of energetic or structural measures. The vector-based perspective of the chemical bonding, constructed using the most preferred direction of charge density accumulation, finds the presence of induced symmetry-breaking for α,ω-disubstituted [4]cumulenes as the end groups are torsioned. The stress tensor trajectories Tσ(s) are used to provide the additional symmetry-breaking required to quantify the degree and nature of the chirality and helical character. We find an absence of chirality for [4]cumulene but a very significant degree of axiality as demonstrated by the purely axial form of the Tσ(s) indicating a lack of helical character. The S-1,5-dimethyl-[4]cumulene contains a very low degree of chiral character but significant axiality(helicity) resulting in a weakly helical morphology of the corresponding Tσ(s). The (-)S(-), (+)S(-) and (+)S(+) conformations of S-1,5-diamino-[4]cumulene contain very significant degrees of both chirality and helical character resulting in helical morphology of the corresponding Tσ(s). The chirality assignments are in agreement with the Cahn–Ingold–Prelog (CIP) classifications for the (-)S(-), (+)S(-) and (+)S(+) conformations of S-1,5-diamino-[4]cumulene. We discuss the consequences for the Tσ(s) in locating chiral character in these molecules in future experiment investigations.



2021 ◽  
pp. 109987
Author(s):  
Soyeong Jeong ◽  
Hwanil Je ◽  
Ji Hyun Lee ◽  
Seung Hun Lee ◽  
Soo-Young Jang ◽  
...  


2021 ◽  
pp. 753-804 ◽  
Author(s):  
Andrew B. Lowe ◽  
Elena Dallerba
Keyword(s):  


Biomolecules ◽  
2021 ◽  
Vol 11 (10) ◽  
pp. 1544
Author(s):  
Dmitry Korolev ◽  
Viktor Postnov ◽  
Ilia Aleksandrov ◽  
Igor Murin

This review presents the main patterns of synthesis for theranostics platforms. We examine various approaches to the interpretation of theranostics, statistics of publications drawn from the PubMed database, and the solid-state and medicinal chemistry methods used for the formation of nanotheranostic objects. We highlight and analyze chemical methods for the modification of nanoparticles, synthesis of spacers with functional end-groups, and the immobilization of medicinal substances and fluorophores. An overview of the modern solutions applied in various fields of medicine is provided, along with an outline of specific examples and an analysis of modern trends and development areas of theranostics as a part of personalized medicine.



2021 ◽  
Author(s):  
Eliot Woods ◽  
Alexandra Berl ◽  
Leanna Kantt ◽  
Christopher Eckdahl ◽  
Michael Wasielewski ◽  
...  

π-Conjugated polymers can serve as active layers in flexible and lightweight electronics, and are conventionally synthesized by transition-metal-mediated polycondensation at elevated temperatures. We recently reported a photopolymerization of electron-deficient heteroaryl Grignard monomers that enables the catalyst-free synthesis of n-type π-conjugated polymers. Herein we provide an experimental and computational investigation of the mechanism of this photopolymerization. Spectroscopic studies performed <i>in situ</i> and after quenching reveal that the propagating species is a radical anion with halide end groups. DFT calculations for model oligomers suggest a Mg-templated S<sub>RN</sub>1-type coupling, in which Grignard monomer coordination to the radical anion chain avoids the formation of free sp<sup>2</sup> radicals and enables C–C bond formation with very low barriers. We find that light plays an unusual role in the reaction, photoexciting the radical anion chain to shift electron density to the termini and thus favor productive monomer binding.



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